CN108054396B - Nitrogen-doped graphene/cobaltous oxide composite material and preparation method thereof - Google Patents
Nitrogen-doped graphene/cobaltous oxide composite material and preparation method thereof Download PDFInfo
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- CN108054396B CN108054396B CN201711350218.XA CN201711350218A CN108054396B CN 108054396 B CN108054396 B CN 108054396B CN 201711350218 A CN201711350218 A CN 201711350218A CN 108054396 B CN108054396 B CN 108054396B
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- H01M4/90—Selection of catalytic material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a nitrogen-doped graphene/cobaltous oxide composite material, which is prepared by taking graphite oxide, a cobalt acetate solution and ammonium carbonate as main raw materials and loading cobaltous oxide on nitrogen-doped graphene by adopting a water bath-hydrothermal-calcining method. The invention firstly proposes that the nitrogen-doped graphene and the cobaltous oxide are compounded, the cobaltous oxide in the obtained composite material has high purity and has synergistic effect with the nitrogen-doped graphene, the composite material has excellent catalytic capability on the cathode oxygen reduction reaction of a fuel cell, and simultaneously the cost of a catalyst material can be greatly reduced.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to a nitrogen-doped graphene/cobaltous oxide composite material and a preparation method thereof.
Background
With the development of society, non-renewable energy sources such as coal, petroleum and the like are gradually reduced, and the use of a large amount of fossil energy sources also causes various environmental problems, thus hindering the development of human socioeconomic. Therefore, it is very necessary to find new clean energy. The fuel cell can directly convert chemical energy into electric energy, is not limited by Carnot cycle, has higher energy conversion efficiency, and is considered to be one of novel environment-friendly and efficient power generation technologies in the 21 st century.
Since the fuel cell converts chemical energy into electrical energy through chemical reaction of the cathode and anode materials, the rate of the chemical reaction becomes a key to limit the energy conversion efficiency of the fuel cell. The oxygen reduction reaction process at the cathode of the fuel cell is complicated, and therefore a catalyst is usually added to the fuel cell to promote the Oxygen Reduction Reaction (ORR) at the cathode of the fuel cell. At present, platinum and platinum-based catalysts are basically used in fuel cells. Due to the world's limitations on platinum resources, the large scale development of platinum-based fuel cells is limited by resource and cost issues. Therefore, the method has important significance in searching high-efficiency electrocatalysts which are rich in resources, low in price and small in environmental pollution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nitrogen-doped graphene/cobaltous oxide composite material, the composite material loads cobaltous oxide on the nitrogen-doped graphene, the obtained composite material has excellent catalytic capability on the cathode oxygen reduction reaction of a fuel cell, the cost of a catalyst material is greatly reduced, and the related preparation method is simple and is suitable for popularization and application.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
a preparation method of a nitrogen-doped graphene/cobaltous oxide composite material comprises the following steps:
1) ultrasonically dispersing graphite oxide in water to obtain GO (graphene oxide) dispersion liquid;
2) dissolving cobalt acetate in water, and uniformly stirring to obtain a cobalt acetate solution; dissolving ammonium carbonate in water, and uniformly mixing to obtain an ammonium carbonate solution;
3) successively adding the obtained cobalt acetate solution and ammonium carbonate solution into the GO dispersion liquid, and uniformly stirring to obtain a mixed solution;
4) condensing and refluxing the obtained mixed solution in a water bath under the stirring condition;
5) naturally cooling the product obtained in the step 4) to room temperature, then carrying out hydrothermal reaction, and carrying out centrifugal separation, washing, freeze-drying and grinding on the product to obtain powder;
6) calcining the powder obtained in the step 5) in an inert atmosphere to obtain the nitrogen-doped graphene/cobaltous oxide composite material.
In the scheme, the graphite oxide is prepared by adopting an improved Hummers method.
In the above scheme, the ultrasonic dispersion step is: ultrasonic processing for 0.5-1h, stirring for 0.5-1h, and ultrasonic processing for 0.5-1 h.
In the scheme, the mass of the graphite oxide and the cobalt acetate is 1 (0.7-2.2).
In the scheme, the mass ratio of the graphite oxide to the ammonium carbonate is 1 (10-40).
In the scheme, the concentration of the graphene oxide in the mixed solution obtained in the step 3) is 0.5-1 mg/ml.
In the scheme, the water bath temperature in the step 4) is 60-80 ℃, and the condensation reflux time is 4-10 h.
In the scheme, the hydrothermal reaction temperature is 120-180 ℃, and the time is 3-12 h; after the hydrothermal reaction is finished, centrifugal separation is carried out, the product is washed 3-5 times by deionized water and is freeze-dried by a freeze dryer.
In the scheme, the calcination temperature is 500-800 ℃, and the time is 2-6 h.
In the above scheme, the inert atmosphere is a nitrogen atmosphere or the like.
The nitrogen-doped graphene/cobaltous oxide composite material is prepared according to the scheme.
The principle of the invention is as follows:
the invention adopts a water bath-hydrothermal-calcining method to prepare the nitrogen-doped graphene/cobaltous oxide composite material: graphite oxide, cobalt acetate solution and ammonium carbonate are used as main raw materials, ammonium ions in the ammonium carbonate can provide nucleation centers for cobalt ions in a water bath process, and carbonate ions and the cobalt ions are combined to form cobalt carbonate, so that the cobalt carbonate grows on the surface of the graphene oxide; in the hydrothermal process, on one hand, ammonium carbonate interacts with graphene oxide to enable nitrogen atoms in ammonium ions to enter crystal lattices of the graphene oxide and enable oxygen-containing functional groups of the graphene oxide to fall off to form nitrogen-doped graphene, on the other hand, cobalt carbonate continuously grows at nucleation centers on the nitrogen-doped graphene to form high-purity cobalt carbonate particles with a certain size (the formation of partial cobalt hydroxide can be effectively avoided), and a nitrogen-doped graphene/cobalt carbonate compound is formed; in the calcining process, carbon dioxide is removed from cobalt carbonate to form cobaltous oxide, and the nitrogen-doped graphene is further reduced, so that the conductivity and stability of the material are improved, and finally the nitrogen-doped graphene/cobaltous oxide composite material is formed.
The composite material obtained by the invention takes the nitrogen-doped graphene as a carrier, and provides more active sites by doping heteroatom nitrogen, so that the catalytic efficiency of the oxygen reduction reaction is effectively improved; cobaltous oxide is used as a transition metal oxide and is an oxygen reduction reaction catalytic material with excellent performance; the two are effectively combined, so that the catalytic efficiency of the oxygen reduction reaction can be further effectively improved.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, a water bath-hydrothermal-calcination method is adopted, graphite oxide, a cobalt acetate solution and ammonium carbonate are used as main raw materials, the nitrogen element doping and the formation of a high-purity ammonium carbonate precursor are synchronously realized by utilizing the interaction between the ammonium carbonate and graphene oxide, the purity of cobaltous oxide in the obtained nitrogen-doped graphene/cobaltous oxide composite material is high, and the obtained nitrogen-doped graphene/cobaltous oxide composite material is compounded with the nitrogen-doped graphene, so that the catalytic performance of the composite material is effectively improved.
2) The invention adopts cobaltous oxide to replace the commonly used noble metal catalytic material, and can effectively reduce the cost of the catalyst material.
3) The preparation process of the composite material is simple and easy to implement, and the experiment repeatability is good.
4) The obtained composite material has excellent catalytic capability on oxygen reduction reaction, and provides a new idea for exploring a high-efficiency electro-catalytic material.
Drawings
FIG. 1 is an XRD pattern of the product prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the nitrogen-doped graphene/cobaltous oxide composite material prepared in example 1 of the present invention, wherein a) is 200nm in scale bar, and b) is 1 μm in scale bar.
Fig. 3 is a TEM image of the nitrogen-doped graphene/cobaltous oxide composite material prepared in example 1 of the present invention, wherein a) is 5nm in scale bar, and b) is 200nm in scale bar.
FIG. 4 is an XPS plot of the product of example 1 of the present invention, wherein a) is a full spectrum analysis plot and b) is a plot of a N1s peak fit.
Fig. 5 is a polarization curve diagram of a working electrode prepared from the nitrogen-doped graphene/cobaltous oxide composite material prepared in example 1 of the present invention at a rotation speed of 1600 rpm.
Detailed Description
For a better understanding of the present invention, reference will now be made to the following examples. It should be noted, however, that the present invention is not limited to the following embodiments.
In the following examples, the graphite oxide was prepared by a modified Hummers method, which specifically includes the following steps: 120ml of concentrated H are added into a three-neck round-bottom flask in sequence2SO4、1.5g NaNO3And 3g of graphite powder, stirring for 0.5h under the ice bath condition, and slowly adding 9g of KMNO4The system temperature is maintained near 0 ℃, and the reaction is carried out for 2 hours at a low temperature; removing the flask from the ice water, slowly dropwise adding a certain amount of deionized water, keeping the temperature of the system at about 35 ℃, stirring for 2 hours, adding a certain amount of deionized water preheated to 98 ℃ into the system, transferring the flask into a water bath pot, heating to raise the temperature of the system to 98 ℃, reacting at high temperature for 15 minutes, taking out the flask, adding a proper amount of H2O2Finally, washing, centrifuging and freeze-drying to obtain the graphite oxide.
Example 1
A preparation method of a nitrogen-doped graphene/cobaltous oxide composite material comprises the following steps:
1) adding 100mg of graphite oxide into deionized water, performing ultrasonic dispersion for 1 hour, stirring for 0.5 hour, and performing ultrasonic dispersion for 1 hour again to form a GO dispersion liquid;
2) respectively dissolving 100mg of cobalt acetate tetrahydrate and 4g of ammonium carbonate in deionized water to prepare a uniform aqueous solution, sequentially adding the prepared cobalt acetate solution and ammonium carbonate solution into GO dispersion liquid and stirring for 0.5h, putting the obtained mixed solution (the concentration of graphene oxide is 0.5mg/ml) into a 500ml two-neck flask, putting the flask into a water bath kettle preheated to 80 ℃, continuously stirring and carrying out condensation reflux for 10 h; after the water bath is finished, taking out the flask, continuously stirring and naturally cooling the solution; filling the cooled solution into a polytetrafluoroethylene lining, filling the lining into a reaction kettle, heating to 180 ℃ for hydrothermal reaction for 3 hours, centrifuging after the reaction is finished, washing a centrifugal product to be neutral by using deionized water, and freeze-drying;
3) grinding the freeze-dried product into powder, loading the powder into a tube furnace, heating to 500 ℃ in a nitrogen atmosphere, calcining, and preserving heat for 2 hours to finally obtain the nitrogen-doped graphene/cobaltous oxide composite material.
The product obtained in this example was subjected to X-ray diffraction analysis, and the results are shown in fig. 1, and in contrast to the standard cobaltous oxide card, the diffraction peaks were found to be completely coincident. Fig. 2 and 3 are scanning electron micrographs and transmission electron micrographs of the product obtained in this example, and it can be seen that cobaltous oxide is successfully attached to the surface of graphene. Fig. 4 is an XPS chart of the obtained product, which shows that the preparation process successfully realizes nitrogen doping, and that the peak fitting is performed on the nitrogen element in the composite material, and that the nitrogen element in the composite material is mainly based on the pyridine nitrogen and pyrrole nitrogen types.
Application example
5mg of the composite material obtained in the embodiment is weighed in a sample tube, and 250 μ L of isopropanol, 750 μ L of deionized water and 20 μ L of Nafion raw solution with the mass fraction of 5% are added. And (3) placing the mixture in an ice-water bath environment, and carrying out ultrasonic treatment for 20min in a cell crusher to obtain uniformly dispersed slurry. And taking 20 mu L of the obtained slurry by using a liquid transfer gun, dripping the slurry on the surface of a glassy carbon electrode, and airing the slurry under the irradiation of an ultraviolet lamp. And mounting the obtained glassy carbon electrode on a rotating disk electrode for electrochemical test.
The polarization curve diagram of the working electrode obtained in the embodiment at the rotating speed of 1600 rpm is shown in fig. 5, and it can be seen that the half-wave potential of the obtained composite material at the rotating speed of 1600 rpm is 0.85, which is close to the half-wave potential of the Pt/C catalyst at the same rotating speed, and has excellent catalytic performance.
Examples 2 to 4
The preparation methods of the nitrogen-doped graphene/cobaltous oxide composite materials described in the embodiments 2 to 4 are substantially the same as those of the embodiment 1, except that: the amounts of ammonium carbonate used in step 2) were 1g (example 2), 2g (example 3) and 3g (example 4), respectively.
In comparative examples 1 to 4, it was found from the results of the elemental analysis test that the contents of N element in examples 1 to 4 were 5.69%, 4.51%, 5.17% and 5.46%, respectively. The results show that: the increase of the content of ammonium carbonate can improve the nitrogen content in the composite material, but the increase trend of the nitrogen content of the composite material is gradually slowed down along with the increase of the content of ammonium carbonate; the nitrogen content in the composite material is increased, so that more active sites can be provided for the catalytic process, and the oxygen reduction catalytic performance of the composite material is improved.
Examples 5 to 8
Examples 5-8 the other parameter steps are the same as in example 1, except that: the amounts of cobalt acetate tetrahydrate used in step (2) were 150mg (example 5), 200mg (example 6), 250mg (example 7) and 300mg (example 8), respectively.
Comparing example 1 with examples 5 to 8, it is shown that the presence of an excessive amount of cobaltous oxide affects the conductivity properties of the composite material and the tendency of the oxygen reduction catalyst properties of the composite material to increase.
Examples 9 to 11
Examples 9-11 the other parameter steps are the same as in example 1, except that: the hydrothermal reaction time in step (2) was 6h (example 9), 9h (example 10) and 12h (example 11), respectively.
Comparing example 1 with examples 9 to 11, it can be seen that the longer the hydrothermal reaction is in the experimental process, the larger the cobaltous oxide particle grows, and the too large particles are easy to fall off on the graphene, which affects the enhancement tendency of the catalytic activity of the composite material.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention are all equivalent substitutions included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a nitrogen-doped graphene/cobaltous oxide composite material is characterized by comprising the following steps:
1) ultrasonically dispersing graphite oxide in water to obtain a graphene oxide dispersion liquid;
2) dissolving cobalt acetate in water, and uniformly stirring to obtain a cobalt acetate solution; dissolving ammonium carbonate in water, and uniformly mixing to obtain an ammonium carbonate solution;
3) successively adding the obtained cobalt acetate solution and ammonium carbonate solution into the graphene oxide dispersion liquid, and uniformly stirring to obtain a mixed solution;
4) condensing and refluxing the obtained mixed solution in a water bath under the stirring condition;
5) naturally cooling the product obtained in the step 4) to room temperature, then carrying out hydrothermal reaction, and carrying out centrifugal separation, washing, freeze-drying and grinding on the product to obtain powder; the hydrothermal reaction temperature is 120-180 ℃;
the mass ratio of the graphite oxide to the ammonium carbonate is 1 (10-40);
6) calcining the powder obtained in the step 5) in an inert atmosphere to obtain the nitrogen-doped graphene/cobaltous oxide composite material.
2. The method of claim 1, wherein the ultrasonic dispersion step is: ultrasonic processing for 0.5-1h, stirring for 0.5-1h, and ultrasonic processing for 0.5-1 h.
3. The preparation method according to claim 1, wherein the mass of the graphite oxide and the cobalt acetate is 1 (0.7-2.2).
4. The preparation method according to claim 1, wherein the concentration of the graphene oxide in the mixed solution obtained in the step 3) is 0.5 to 1 mg/ml.
5. The preparation method of claim 1, wherein the water bath temperature in the step 4) is 60-80 ℃, and the condensation reflux time is 4-10 h.
6. The preparation method according to claim 1, wherein the hydrothermal reaction time is 3-12 h.
7. The method as claimed in claim 1, wherein the calcination temperature is 500-800 ℃ and the calcination time is 2-6 h.
8. The nitrogen-doped graphene/cobaltous oxide composite material prepared by the preparation method of any one of claims 1 to 7.
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| CN111987327B (en) * | 2020-08-26 | 2022-07-08 | 福州大学 | Pt/Co nanoparticle-loaded nitrogen-doped graphene and preparation method thereof |
| CN112846212B (en) * | 2021-01-04 | 2023-02-21 | 宇辰新能源材料科技无锡有限公司 | High-thermal-conductivity cobalt powder and preparation method thereof |
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